Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
  • C09B67/0008—Coated particulate pigments or dyes with organic coatings
  • C09B67/0009—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives
  • C09B67/001—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives containing resinic acid derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B17/00—Azine dyes

Definitions

• the present invention relates to novel pigment compositions, to processes for the preparation thereof and to the use thereof for producing coloured engineering plastics (thermoplastics that maintain dimensional stability and most mechanical properties above 100° C. or below 0° C.), especially those based on polyamide.
• coloured engineering plastics thermoplastics that maintain dimensional stability and most mechanical properties above 100° C. or below 0° C.
• Mass-colouring of polymer processed at high temperatures, such as engineering plastics and in particular polyamides is usually carried out using so-called solvent dyes, which are soluble in the polyamide mass at high processing temperatures and which, besides having the requisite high heat resistance, also have adequate chemical stability with respect to, for example, the highly reductive medium of the polyamide melt.
• solvent dyes which are soluble in the polyamide mass at high processing temperatures and which, besides having the requisite high heat resistance, also have adequate chemical stability with respect to, for example, the highly reductive medium of the polyamide melt.
• soluble dyes generally have much poorer lightfastness, as compared with pigments.
• pigments in such polymers are restricted almost exclusively to inorganic pigments, most of which contain heavy metals, and to a very small selection of specific organic pigments, mainly from the phthalocyanine or quinacridone class.
• Inorganic pigments however, have generally low chroma and low colour strength.
• Organic pigments have disadvantages such as crystal phase and colour changes, migration, a frequent tendency of the coloured materials to fluoresce, and often a reactive interaction with the polymer, leading to degradation of the pigment and/or deterioration of the polymer's mechanical properties.
• U.S. Pat. No. 3,826,670 discloses encapsulated pigments with an intermediate ionically crosslinked polymeric salt and a skin consisting essentially of dense, amorphous, hydrated oxide or hydroxide of silicon, titanium or zirconium.
• WO 06/111 493 is a patent application according to Art. 54(3) EPC and Rule 64.3 PCT, which is directed to pigments encapsulated by polymers which are not crosslinked.
• R 1 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or COOR 5
• R 2 and R 3 are independently from one another H
• R 4 , R 5 and R 6 are independently from one another H, unsubstituted C 1 -C 6 alkyl or C 2 -C 6 alkenyl, or C 2 -C 6 alkyl or C 2 -C 6 alkenyl each substituted by one or more hydroxy and/or epoxy groups
• n is a number from 2 to 2000, preferably from 5 to 1500.
• the organic pigment is either directly embedded in the crosslinked polymer, or it is chemically or physically surface-modified or encapsulated, for example with a pigment derivative, a polymer or a layer of one or more transition metal oxides adsorbed on or bound to its surface.
• the pigment and any optional additional components should be fully surrounded by crosslinked polymer, as the surface of the solid particles should consist essentially of the crosslinked polymer, in order the desired properties to be obtained.
• Suitable prepolymers are known and a large choice thereof is available commercially, too. Suitable prepolymers are for example disclosed in WO 01/74 735. Commercially available self crosslinking prepolymers are for example Acronal® LR 8977, Acronal® S 760 na (both BASF AG, Ludwigshafen/DE) and Glascol® C 44 (CIBA Specialty Chemicals Inc.).
• the crosslinking reaction can take place simply at room temperature, such as in the case of aqueous acrylic prepolymer dispersions to which bishydrazides or aziridines are subsequently added, or at elevated temperature, such as from 50 to 300° C., especially from 130 to 200° C., optionally in the presence of a suitable catalyst, for example acids, metal compounds, amines, ammonium or hydroxy ions, such as hydrochloric acid, dibutyl tin laurate, triethylamine or tetrabutylammonium iodide.
• a suitable catalyst for example acids, metal compounds, amines, ammonium or hydroxy ions, such as hydrochloric acid, dibutyl tin laurate, triethylamine or tetrabutylammonium iodide.
• the instant pigment compositions generally comprise pigment particles having a size of from 0.01 to 10 ⁇ m, preferably up to 5 ⁇ m, most preferred from 0.05 to 2 ⁇ m, especially from 0.1 to 1 ⁇ m.
• the capsules comprising the pigment preferably have an average volume from 10 ⁇ 20 to 10 ⁇ 8 m 3 , especially from 10 ⁇ 18 to 10 ⁇ 10 m 3 .
• the instant pigment compositions comprise adequately from 0 to 20% by weight of other components, preferably from 0 to 3% by weight of volatile components, most preferred up to 2% by weight of volatile components, based on the total pigment composition.
• the volatile components preferably consist of organic solvents or water, most preferred water.
• Any organic pigment can be used, for example diketopyrrolopyrrole, quinacridone, azo, quinophthalone, phthalocyanine, indanthrone, flavanthrone, pyranthrone, anthraquinone, perylene, dioxazine, perinone, thioindigo, isoindolinone, isoindoline, pteridine and metal complex pigments.
• R 7 and R 8 are each independently of the other a group of formula
• R 32 , R 33 , R 34 and R 35 are each independently of one another NH 2 , OH, hydrogen, C 1 -C 4 alkyl, NHR 36 , N(R 36 ) 2 or
• phenyl biphenyl or naphthyl which are each unsubstituted or substituted by halogen, OH, NH 2 , C 1 -C 4 alkyl or C 1 -C 4 alkoxy, preferably NH 2 , OH, hydrogen, methyl, ethyl, NHCOR 37 , NHCOOR 37 , NHCONHR 37 , NHCONR 36 R 37 or phenyl which is unsubstituted or substituted by OH or NH 2 , most preferred NH 2 , OH, hydrogen, methyl, NHCOR 37 or phenyl which is unsubstituted or substituted by NH 2 , wherein
• R 38 is a group
• C 2 -C 12 Alkenyl or C 3 -C 12 cycloalkenyl is respectively C 2 -C 12 alkyl or C 3 -C 12 cycloalkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated, for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen
• the pigments preferably have a specific surface area of from 10 to 150 m 2 /g. Special preference is given to opaque pigments having a specific surface area of from 12 to 50 m 2 /g and to transparent pigments having a specific surface area of from 50 to 100 m 2 /g.
• the instant pigment compositions are suitably prepared by dispersing the pigment and the prepolymer in an inert liquid medium, such as an organic solvent or preferably water, then crosslinking the prepolymer by addition of a crosslinking agent, addition of a crosslinking catalyst and/or heating.
• an inert liquid medium such as an organic solvent or preferably water
• the instant pigment compositions are then preferably isolated by filtration and dried.
• Crosslinking or optionally the final part of crosslinking, can also be effected upon final processing of the engineering plastic to be coloured.
• Colouring the engineering plastics with the pigment composition according to the invention is carried out, for example, by mixing such a pigment composition into the substrates using roll mills or mixing or grinding apparatuses, as a result of which the pigment composition is finely distributed in the engineering plastic.
• the high engineering plastic comprising the admixed pigment composition is then processed by methods known per se, such as calendering, compression moulding, extrusion, spread-coating, melt-spinning, casting or by injection moulding, whereby the coloured material acquires its final shape.
• the instant pigment compositions largely retain their structure upon processing, so that the instant crosslinked polymer remains around the pigments, thus preventing a direct contact between the pigment and the engineering plastic.
• the instant pigment compositions also have an excellent compatibility with engineering plastics.
• plasticisers In order to produce non-rigid mouldings or to reduce their brittleness, it is possible to incorporate so-called plasticisers into the engineering plastics prior to shaping.
• plasticisers for example, esters of phosphoric acid, phthalic acid or sebacic acid.
• the plasticisers may be incorporated into the polymers before or after incorporation of the colorant.
• further pigments or other colorants in any desired amounts, optionally together with further additional ingredients such as, for example, fillers or siccatives (drying agents).
• Preferred engineering plastics suitable for colouring in accordance with the invention are very generally polymers having a dielectric constant 2.5 at 20° C., preferably polyester (e.g. PET), polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadiene/styrene (ABS).
• polyester e.g. PET
• PC polycarbonate
• PS polystyrene
• PMMA polymethyl methacrylate
• polyamide polyethylene
• polypropylene styrene/acrylonitrile
• ABS acrylonitrile/butadiene/styrene
• polyester Special preference is given to polyester and very special preference is given to polyamide, for example polyamide 6, polyamide 6.6, polyamide 12 and aramid.
• the pigment compositions according to the invention are well dispersible in the afore-mentioned materials, especially polyamides, and provide them with strongly coloured, level hues and in-use fastness properties, especially thermal stability, lightfastness, migration fastness and washing fastness, without fluorescence and deterioration of the mechanical properties.
• Acronal® S 760 50 ⁇ 1% solids, BASF
• the polymer is then precipitated by the addition of HCl, and the solids are filtered and dried at 60° C./10 4 Pa.
• Test plates made of polyamide 6 (Ultramid® B3K, BASF) containing 0.2% of the encapsulated pigments according to examples 1-3 are prepared by injection molding from a pre-concentrate compounded in a twin-screw extruder. The processing temperatures are between 240 and 300° C. So produced test plates show excellent temperature and light stability, as well as excellent wash stability, no migration of the colorants and no fluorescence.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)
• Coloring (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2007
  • 2007-10-15 JP JP2009533788A patent/JP2010507698A/ja active Pending
  • 2007-10-15 CN CN200780039532.4A patent/CN101528857B/zh active Active
  • 2007-10-15 CN CN200780039356.4A patent/CN101528861B/zh active Active
  • 2007-10-15 US US12/446,250 patent/US8461229B2/en active Active
  • 2007-10-15 KR KR1020097010584A patent/KR101530866B1/ko active IP Right Grant
  • 2007-10-15 ES ES07821311.3T patent/ES2553186T3/es active Active
  • 2007-10-15 WO PCT/EP2007/060944 patent/WO2008049749A1/en active Application Filing
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